WO2017105784A1 - Processes for removing nitriles from a feed to an oligomerization zone - Google Patents
Processes for removing nitriles from a feed to an oligomerization zone Download PDFInfo
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- WO2017105784A1 WO2017105784A1 PCT/US2016/063035 US2016063035W WO2017105784A1 WO 2017105784 A1 WO2017105784 A1 WO 2017105784A1 US 2016063035 W US2016063035 W US 2016063035W WO 2017105784 A1 WO2017105784 A1 WO 2017105784A1
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0423—Beds in columns
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
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- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
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- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/12—Recovery of used adsorbent
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
- B01D2259/40092—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot liquid
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- This invention relates generally to processes for removing contaminants from a feed stream to a reaction zone, and more particularly to processes for removing nitriles from a feed stream to an oligomerization zone.
- oligomerization processes process a feed stream comprising C4/C5 olefins and convert these components into diesel range products, as well as some gasoline blending components.
- the stream comprising C4/C5 olefins may originate from a fluidized catalytic cracking (FCC) unit.
- FCC fluidized catalytic cracking
- the oligomerization of the C4/C5 olefins from an FCC utilize a catalyst that is sensitive to many contaminants contained in the feed stream. Accordingly, the feed stream to an oligomerization zone is typically treated in a pretreatment section to remove the various contaminants and inhibitors.
- a pretreatment section contains various removal zones each configured to remove contaminants, such as sulfur compounds, di-olefins, oxygenates, nitriles or other contaminants or inhibitors that may be in the feed stream.
- a nitrile removal zone typically includes a nitrile removal unit (NRU) which is used to remove the trace levels of nitriles contained in the feed stream.
- the NRU is typically a swing bed adsorption system that requires an external regenerant stream to refresh the adsorbent bed by desorbing or removing the nitriles from the adsorbent.
- the regenerant stream is typically a C4 or C5 hydrocarbon stream that is free of these contaminants.
- This regenerant stream is vaporized and the spent adsorbent bed is heated with the vaporized stream and the contaminants are removed from the adsorbent.
- the unwanted contaminants, removed from the feed stream, are now transferred to the spent regenerant stream and the refreshed adsorbent bed is ready to be placed back on-line.
- regenerant stream may comprise portion of an effluent from a reaction zone, such as an oligomerization zone or a hydrotreating zone.
- the spent regenerant comprising the desorbed nitriles maybe combined with the reactor effluent and separated in a separation zone along with the effluent into a least one stream including the nitriles.
- the present invention may be characterized broadly as providing a process for removing nitriles from a feed stream for a reaction zone by: adsorbing nitriles from a feed stream in a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; oligomerizing the cleaned feed stream in an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; and, desorbing the nitriles from the nitrile removal zone with a regenerant stream comprising a hot liquid to provide a spent regenerant stream.
- the regenerant stream comprises a portion of the oligomerized effluent.
- the regenerant stream comprises a portion of a hydrotreated effluent.
- the feed stream comprises C3 to C7 hydrocarbons.
- the process includes separating the oligomerized effluent in a separation zone into a C4- stream, a diesel stream, and a gasoline stream.
- the separation zone includes at least two columns and a first column from the at least two columns provides the C4- stream and a second column from the at least two columns provides the diesel stream and the gasoline stream.
- the second column further provides the regenerant stream.
- the regenerant stream comprises a sidecut stream from the second column, wherein the sidecut stream comprises C8 to C12 hydrocarbons.
- the process includes separating the spent regenerant stream into at least one stream including nitriles. It is contemplated that the spent regenerant stream is separated in a separation column with the oligomerized effluent.
- the present invention may be broadly characterized as providing a process for removing nitriles from a feed stream for a reaction zone by: passing a feed stream comprising hydrocarbons and nitriles to a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; passing the cleaned feed stream to an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; passing the oligomerized effluent to a separation zone being configured to provide at least one C4- stream and at least one product stream; and, passing a regenerant stream comprising a hot liquid to the nitrile removal zone to desorb the nitriles and provide a spent regenerant stream, the spent regenerant stream including nitriles.
- the regenerant stream comprises a portion of
- the regenerant stream comprises a portion of the oligomerized effluent. It is contemplated that the feed stream comprises a C3 to C7 hydrocarbon feed stream.
- the separation zone comprises at least two columns, wherein a first column provides the C4- stream, and wherein a second column provides the at least one product stream. It is contemplated that the second column provides the regenerant stream. It is further contemplated that the process includes passing the spent regenerant stream to the first column of the separation zone. It is even further contemplated that the spent regenerant stream and the oligomerized effluent are combined before being passed into the first separation column. It is contemplated that the regenerant stream comprises a C8 to C12 hydrocarbon stream. It is further contemplated that the feed stream comprises a portion of an effluent from a catalytic cracking zone.
- the Figure shows a process flow diagram according to one or more embodiments of the present invention.
- the nitrile removal zone is preferably disposed upstream of a reaction zone, and the regenerant may comprises a portion of the effluent from the reaction zone.
- the reaction zone comprises an oligomerization zone, and the regenerant comprises a portion of the oligomerized effluent.
- a stream of other liquid may be used as the regenerant, such as a portion of a hydrotreated effluent.
- Such hot liquid streams are readily available in most applications. Additionally, the use of such a stream allows for the spent regenerant in some instances to be separated along with the reactor effluent.
- a feed stream 10 for a reaction zone for example, an oligomerization zone 12 is first passed to a pretreatment zone 14 that includes various units 16a, 16b, 16c for removing contaminants.
- a pretreatment zone 14 that includes various units 16a, 16b, 16c for removing contaminants.
- the feed stream 10 is preferably a portion of a cracked effluent, for example, a portion of an effluent from a fluid catalytic cracking (FCC) process.
- the FCC process typically produces a significant quantity of light olefins, for example, the total yield of C4 and C5 olefins from an FCC unit can be 20 wt% or more of the fresh feed.
- the C4 and C5 olefins are typically low value products. Accordingly, there is often a desire to convert these olefins into more desired product like diesel via oligomerization.
- hydrocarbon molecules may be abbreviated CI, C2, C3 . . . Cn where "n" represents the number of carbon atoms in the one or more hydrocarbon molecules.
- a superscript "+” or “-” may be used with an abbreviated one or more hydrocarbons notation, e.g., C4+ or C4-, which is inclusive of the abbreviated one or more hydrocarbons.
- C4+ means one or more hydrocarbon molecules of three carbon atoms and/or more.
- the feed stream 10 may also include light hydrocarbons, for example C3 hydrocarbons, as well as heavier hydrocarbons, such as C6 to C7 hydrocarbons.
- the C4 hydrocarbons includes butenes, i.e., C4 olefins, and butanes. Butenes include normal butenes and isobutene.
- the C5 hydrocarbons includes pentenes, i.e., C5 olefins, and pentanes. Pentenes include normal pentenes and isopentenes.
- the feed stream 10 will comprise 20 to 80 wt% olefins and suitably 40 to 75 wt% olefins. In an aspect, 55 to 75 wt% of the olefins may be butenes and 25 to 45 wt% of the olefins may be pentenes. Additionally, 10 wt%, suitably 20 wt%, typically 25 wt% and most typically 30 wt% of the feed may be C5 olefins. In addition to the hydrocarbons, the feed stream 10 includes sulfur compounds, di-olefins, oxygenates, nitriles, each of which is removed or converted in the units 16a, 16b, 16c in the pretreatment zone 14.
- One of the units 16a, 16b 16c in the pretreatment zone 14 comprises a nitrile removal zone 18.
- Other units 16a, 16b in the pretreatment zone 14 may include a sulfur removal zone, a selective hydrogenation zone, a water wash, or a bisulfite wash.
- the nitrile removal zone 18 is configured to selectively adsorb nitriles, and possibly some oxygenates, from the feed stream 10 (which may or may not have been subjected to pretreatment in other units 16a, 16b in the pretreatment zone 14) and provide a cleaned feed stream 20 that is relatively free of nitriles.
- the nitrile removal zone 18 can use any suitable adsorbent for removing nitriles from the feed stream 10, which can be, for example, a zeolitic molecular sieve.
- the molecular sieve can include a zeolite X, Y, L, or a combination thereof.
- the adsorption conditions can be 20 to 80 °C (68 to 176 °F) and a pressure of 100 to 3,500 kPa (14.5 to 508 psi).
- Exemplary adsorbent beds and conditions are disclosed in, e.g., U.S. Pat. No. 5,271 ,835.
- the nitrile removal zone 18 may include one or more, preferably two or more, adsorbent beds.
- the nitrile removal zone 18 includes two or three vessels arranged in a lead-lag configuration (not shown), allowing for the feed stream 10 to be processed in one vessel while adsorbent in a second vessel is being regenerated (discussed below).
- the cleaned feed stream 20 is passed to the oligomerization zone 12 which includes at least one oligomerization reactor 22 containing a catalyst and being configured to provide an oligomerized effluent 24.
- the cleaned feed stream 20 may be preheated before entering the oligomerization reactor 22.
- the oligomerization reactor 22 may be an upflow reactor to provide a uniform feed front through the catalyst bed, but other flow arrangements are contemplated.
- the oligomerization reactor 22 may contain an additional bed or beds of oligomerization catalyst.
- C4 olefins in the cleaned feed stream 20 oligomerize over the oligomerization catalyst to provide an oligomerate comprising C4 olefin dimers and trimers.
- C5 olefins in the cleaned feed stream 20 oligomerize over the oligomerization catalyst to provide an oligomerate comprising C5 olefin dimers and trimers and co-oligomerize with C4 olefins to make C9 olefins.
- the oligomerization produces other oligomers with additional carbon numbers.
- the operating conditions of the oligomerization zone 12 include exemplary operating pressures between 2.1 MPa (300 psia) and 10.5 MPa (1,520 psia), or between 2.1 MPa (300 psia) and 6.9 MPa (1,000 psia), or between 2.8 MPa (400 psia) and 4.1 MPa (600 psia). Lower pressures may be suitable if the reaction is kept in the liquid phase.
- the temperature of the oligomerization conditions in the oligomerization zone 12 expressed in terms of a maximum bed temperature is in a range between 150 and 300 °C (302 to 572 °F), or between 200 and 250 °C (392 to 482 °F), or between 225 and 245 °C (437 to 473 °F).
- the space velocity may be between 0.5 and 5.0 hr 1 .
- the exothermic reaction will cause the temperature to rise. Consequently, the oligomerization reactor 22should be operated to allow the temperature at the outlet to be over 25 °C (45 °F) greater than the temperature at the inlet.
- the oligomerized effluent 24 from the oligomerization zone 12 may be passed to a separation zone 26 having one or more separation vessels to provide various product streams.
- the separation zone 26 may comprise two separation columns 28, 30, each of which is a fractionation column.
- the term "column” means a distillation column or columns for separating one or more components of different volatilities. Unless otherwise indicated, each column includes a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottom stream back to the bottom of the column.
- Feeds to the columns may be preheated.
- the top pressure is the pressure of the overhead vapor at the outlet of the column.
- the bottom temperature is the liquid bottom outlet temperature.
- Overhead lines and bottom lines refer to the net lines from the column downstream of the reflux or reboil to the column.
- a first separation column 28 may separate the oligomerized effluent 24 into an overhead stream 32 comprising C4 olefins and hydrocarbons and a liquid bottoms stream 34 comprising C5+ olefins and hydrocarbons.
- the liquid bottoms stream 34 may be passed to the second fractionation column 30 to be separated into different streams, for example a gasoline stream 36, typically comprising C5 to C9 hydrocarbons, and a diesel range stream 38, typically comprising CI O to C16 hydrocarbons.
- the gasoline stream 36 and the diesel range stream 38 may be processed further, for example, the diesel range stream 38 being passed to a hydrotreating zone 39 to remove heteroatoms to provide a diesel fuel stream.
- diesel can include hydrocarbons having a boiling point temperature in the range of 150 to 400 °C (302 to 752 °F) and preferably 200 to 400 °C (392 to 752 °F).
- gasoline can include hydrocarbons having a boiling point temperature in the range of 25 to 200 °C (77 to 392 °F) and at atmospheric pressure.
- the hydrotreating zone 39 includes a hydrotreating reactor 41.
- the hydrotreating zone 39 shown in the Figure has one hydrotreating reactor 41 ; however, more than one hydrotreating reactor 41 may be utilized.
- Each hydrotreating reactor 41 may have one or more beds 43a, 43b of a suitable hydroprocessing catalyst.
- a hydroprocessed diesel stream 45 exits the hydrotreating zone 39.
- the hydrotreating reactor 41 in the hydrotreating zone 39 may be operated in a continuous liquid phase, in a continuous gas phase, or with a mixture of gas and liquid.
- the diesel range stream 38 may be mixed with a hydrogen stream 47 prior to entering the hydrotreating reactor 41.
- hydrogen may be provided to the hydrotreating reactor 41 at one or more hydrogen inlet points (not shown) located downstream of the feed inlet for the diesel range stream 38. The flow rate of hydrogen added at these downstream locations is controlled to ensure that the reactor operates in a continuous liquid phase.
- the diesel range stream 38 does not contain recycled product comprising a portion of the hydroprocessed diesel stream 45 or other hydrocarbon diluent.
- a recycle stream or diluent may be incorporated into the fresh diesel range stream 38 prior to hydrotreating to feed additional volume to the hydrotreating reactor 41 to provide added hydrogen-carrying capacity to the diesel range stream 38 or to provide additional mass to reduce the temperature rise in catalyst beds 43a, 43b.
- any recycled product or diluent typically is introduced into the diesel range stream 38 before the hydrogen in line 47 is mixed with the diesel range stream 38.
- such recycled product may be previously stripped of a vaporous hydrogen sulfide, nitrogen or nitrogen containing compositions, and any other vapor phase materials.
- hydrotreating zone 39 hydrogen gas is contacted with the hydrocarbons in the diesel range stream 38 in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur and nitrogen from the hydrocarbon feedstock. Additionally, unsaturated hydrocarbons are saturated.
- Suitable hydrotreating catalysts for use in the present invention are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and/or nickel and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
- Other suitable hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. It is within the scope of the present invention that more than one type of hydrotreating catalyst be used.
- the Group VIII metal is typically present in an amount ranging from 2 to 20 wt%, preferably from 4 to 12 wt%.
- the Group VI metal will typically be present in an amount ranging from 1 to 25 wt%, preferably from 2 to 25 wt%.
- Suitable hydrotreating reaction conditions include a temperature from 204 to 482 °C (400 to 900 °F), preferably no more than 388 °C (730 °F), a pressure from 3.5 to 17.3 MPa (500 to 2500 psig), preferably no more than 10,342 kPa (1500 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous feedstock (i.e., the diesel range stream 38) from 0.1 hr "1 to 10 hr "1 with a hydrotreating catalyst or a combination of hydrotreating catalysts.
- the hydrotreated diesel stream 45 (i.e., the hydrotreated effluent) has a lower sulfur concentration and an improved cetane number than that of the diesel range stream 38.
- the further processing of the hydrotreated diesel stream 45 is not important to the practicing of the present invention.
- a regenerant stream 40 comprising a hot liquid is utilized to desorb the nitriles.
- hot it is meant that the regenerant stream 40 has a temperature between 175 to 275 °C (347 to 527 °F), or between 200 to 250 °C (392 to 482 °F), or 230 °C (446 °F).
- a regenerant stream comprised vapor, typically with C4/C5 hydrocarbons. Again, such a vapor stream may not be readily available; however, various hot liquid streams having low levels of nitriles are typically readily available in most refineries.
- the regenerant stream 40 may comprise a portion of the oligomerized effluent 24 without further conversion or treating.
- the regenerant stream 40 may comprise a stream from the separation zone 26.
- the regenerant stream 40 comprises a sidecut stream 42 from the second fractionation column 30 in the separation zone 26.
- the sidecut stream 42 comprises a range of C8 to C12 hydrocarbons.
- the use of the oligomerized effluent 24, or a portion thereof may not be desirable, for example depending on the amount of dienes in the sidecut stream 42.
- At least a portion of a hydrotreated effluent is used as the regenerant stream 40.
- a diesel fuel stream 44 from a hydrotreating unit (not shown) be used as the regenerant stream 40. It is contemplated that the diesel fuel stream 44 comprises at least a portion of the diesel range stream 38 that has been hydrotreated, such as the hydrotreated diesel stream 45 from the hydrotreating zone 39.
- Other readily available hot liquid streams may be used in accordance with the present invention as the regenerant stream 40.
- a spent regenerant stream 46 including the desorbed nitriles, may be removed from the nitrile removal zone 18.
- the spent regenerant 46 is combined and passed to the separation zone 26 along with the oligomerized effluent 24.
- the spent regenerant 46 and the oligomerized effluent 24 are combined, it is also contemplated that each is passed into the separation zone 26 independently.
- the nitriles will separate out with the overhead stream 32 of the first fractionation column 28.
- the hydrocarbons in the regenerant will mostly comprise components in the liquid bottoms stream 34 that can be processed and separated as described above.
- the nitriles in the spent regenerant stream 46 may be less than 100 ppm.
- the spent regenerant 46 may be passed to a fuel blending pool (not shown).
- the spent regenerant 46 is passed to the hydrotreating zone 39.
- various processes for regeneration for a nitrile removal zone are provided which utilize a readily available hot liquid regenerant.
- the use of the hot liquid may lower operating utilities since it will not need to be vaporized.
- the process will provide a readily available stream of hot liquid that is relatively free of contaminants.
- the use of the hot liquid allows for the use of existing equipment to separate nitriles from the liquid hydrocarbons of the regenerant.
- a first embodiment of the invention is a process for removing nitriles from a feed stream for a reaction zone, the process comprising adsorbing nitriles from a feed stream in a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; oligomerizing the cleaned feed stream in an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; and, desorbing the nitriles from the nitrile removal zone with a regenerant stream comprising a hot liquid to provide a spent regenerant stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a portion of the oligomerized effluent.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a portion of a hydrotreated effluent.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the feed stream comprises C3 to C7 hydrocarbons.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising separating the oligomerized effluent in a separation zone into a C4- stream, a diesel stream, and a gasoline stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the separation zone includes at least two columns and wherein a first column of the at least two columns provides the C4- stream and wherein a second column of the at least two columns provides the diesel stream and the gasoline stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the second column further provides the regenerant stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a sidecut stream from the second column, wherein the sidecut stream comprises C8 to C12 hydrocarbons.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising separating the spent regenerant stream into at least one stream with nitriles.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the spent regenerant stream is separated in a separation column with the oligomerized effluent.
- a second embodiment of the invention is a process for removing nitriles from a feed stream for a reaction zone, the process comprising passing a feed stream comprising hydrocarbons and nitriles to a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; passing the cleaned feed stream to an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; passing the oligomerized effluent to a separation zone being configured to provide at least one C4- stream and at least one product stream; and, passing a regenerant stream comprising a hot liquid to the nitrile removal zone to desorb the nitriles and provide a spent regenerant stream, the spent regenerant stream including nitriles.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the regenerant stream comprises a portion of a hydrotreated effluent.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the regenerant stream comprises a portion of the oligomerized effluent.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the feed stream comprises a C3 to C7 hydrocarbon feed stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the separation zone comprises at least two columns, wherein a first column provides the C4- stream, and wherein a second column provides the at least one product stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the second column provides the regenerant stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising passing the spent regenerant stream to the first column of the separation zone.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the spent regenerant stream and the oligomerized effluent are combined before being passed into the first separation column.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the regenerant stream comprises a C8 to C12 hydrocarbon stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the feed stream comprises a portion of an effluent from a catalytic cracking zone.
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Abstract
Processes for regenerating adsorbent in a nitrile removal zone. The regenerant comprises a stream of hot liquid that may comprise a portion of the oligomerized effluent or a portion of a hydrotreated effluent. A spent regenerant comprising the desorbed nitriles may be processed along with the oligomerized effluent with existing separation equipment.
Description
PROCESSES FOR REMOVING NITRILES
FROM A FEED TO AN OLIGOMERIZATION ZONE
STATEMENT OF PRIORITY
[0001] This application claims priority to U.S. Application No. 62/267,452 which was filed December 15, 2015, the contents of which are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates generally to processes for removing contaminants from a feed stream to a reaction zone, and more particularly to processes for removing nitriles from a feed stream to an oligomerization zone.
BACKGROUND OF THE INVENTION
[0003] It is known to oligomerize low boiling range olefins into higher value products that have higher boiling points. For example, some oligomerization processes, process a feed stream comprising C4/C5 olefins and convert these components into diesel range products, as well as some gasoline blending components. In some refineries, the stream comprising C4/C5 olefins may originate from a fluidized catalytic cracking (FCC) unit.
[0004] The oligomerization of the C4/C5 olefins from an FCC utilize a catalyst that is sensitive to many contaminants contained in the feed stream. Accordingly, the feed stream to an oligomerization zone is typically treated in a pretreatment section to remove the various contaminants and inhibitors.
[0005] Typically, a pretreatment section contains various removal zones each configured to remove contaminants, such as sulfur compounds, di-olefins, oxygenates, nitriles or other contaminants or inhibitors that may be in the feed stream. Thus, a nitrile removal zone typically includes a nitrile removal unit (NRU) which is used to remove the trace levels of nitriles contained in the feed stream. The NRU is typically a swing bed adsorption system that
requires an external regenerant stream to refresh the adsorbent bed by desorbing or removing the nitriles from the adsorbent.
[0006] In a conventional NRU, the regenerant stream is typically a C4 or C5 hydrocarbon stream that is free of these contaminants. This regenerant stream is vaporized and the spent adsorbent bed is heated with the vaporized stream and the contaminants are removed from the adsorbent. The unwanted contaminants, removed from the feed stream, are now transferred to the spent regenerant stream and the refreshed adsorbent bed is ready to be placed back on-line.
[0007] While these processes are presumably effective for their intended purposes, such regeneration processes rely upon a regenerant stream that may not be readily available in some or most refineries. Additionally, while an externally produced regenerant stream could be used, such streams can be costly.
[0008] Accordingly, it would be desirable to have one or more processes that efficiently and efficiently allow for the regeneration of a nitrile removal zone that do not require a C4/C5 vaporized regenerant stream. It would also be desirable if one or more of such processes utilized a regenerant stream that is readily available in most refineries.
SUMMARY OF THE INVENTION
[0009] One or more processes have been invented in which a hot liquid stream is used to regenerate absorbents in a nitrile removal zone. The regenerant stream may comprise portion of an effluent from a reaction zone, such as an oligomerization zone or a hydrotreating zone. The spent regenerant comprising the desorbed nitriles maybe combined with the reactor effluent and separated in a separation zone along with the effluent into a least one stream including the nitriles.
[00010] In a first aspect of the invention, the present invention may be characterized broadly as providing a process for removing nitriles from a feed stream for a reaction zone by: adsorbing nitriles from a feed stream in a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; oligomerizing the cleaned feed stream in an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; and, desorbing
the nitriles from the nitrile removal zone with a regenerant stream comprising a hot liquid to provide a spent regenerant stream.
[00011] In at least one embodiment, the regenerant stream comprises a portion of the oligomerized effluent.
[00012] In at least one embodiment, the regenerant stream comprises a portion of a hydrotreated effluent.
[00013] In at least one embodiment, the feed stream comprises C3 to C7 hydrocarbons.
[00014] In at least one embodiment, the process includes separating the oligomerized effluent in a separation zone into a C4- stream, a diesel stream, and a gasoline stream. It is contemplated that the separation zone includes at least two columns and a first column from the at least two columns provides the C4- stream and a second column from the at least two columns provides the diesel stream and the gasoline stream. It is also contemplated that the second column further provides the regenerant stream. It is further contemplated that the regenerant stream comprises a sidecut stream from the second column, wherein the sidecut stream comprises C8 to C12 hydrocarbons.
[00015] In at least one embodiment, the process includes separating the spent regenerant stream into at least one stream including nitriles. It is contemplated that the spent regenerant stream is separated in a separation column with the oligomerized effluent.
[00016] In a second aspect of the present invention, the present invention may be broadly characterized as providing a process for removing nitriles from a feed stream for a reaction zone by: passing a feed stream comprising hydrocarbons and nitriles to a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; passing the cleaned feed stream to an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; passing the oligomerized effluent to a separation zone being configured to provide at least one C4- stream and at least one product stream; and, passing a regenerant stream comprising a hot liquid to the nitrile removal zone to desorb the nitriles and provide a spent regenerant stream, the spent regenerant stream including nitriles.
[00017] In at least one embodiment, the regenerant stream comprises a portion of a hydrotreated effluent.
[00018] In at least one embodiment, the regenerant stream comprises a portion of the oligomerized effluent. It is contemplated that the feed stream comprises a C3 to C7 hydrocarbon feed stream.
[00019] In at least one embodiment, the separation zone comprises at least two columns, wherein a first column provides the C4- stream, and wherein a second column provides the at least one product stream. It is contemplated that the second column provides the regenerant stream. It is further contemplated that the process includes passing the spent regenerant stream to the first column of the separation zone. It is even further contemplated that the spent regenerant stream and the oligomerized effluent are combined before being passed into the first separation column. It is contemplated that the regenerant stream comprises a C8 to C12 hydrocarbon stream. It is further contemplated that the feed stream comprises a portion of an effluent from a catalytic cracking zone.
[00020] Additional aspects, embodiments, and details of the invention, all of which may be combinable in any manner, are set forth in the following detailed description of the invention.
DETAILED DESCRIPTION OF THE DRAWINGS
[00021] One or more exemplary embodiments of the present invention will be described below in conjunction with the following drawing figure, in which:
[00022] the Figure shows a process flow diagram according to one or more embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[00023] As mentioned above, one or more processes have been invented for regenerating adsorbent in a nitrile removal zone with a liquid regenerant stream. The nitrile removal zone is preferably disposed upstream of a reaction zone, and the regenerant may comprises a portion of the effluent from the reaction zone. In a preferred embodiment, the reaction zone comprises an oligomerization zone, and the regenerant comprises a portion of the oligomerized effluent.
Alternatively, a stream of other liquid may be used as the regenerant, such as a portion of a hydrotreated effluent. Such hot liquid streams are readily available in most applications. Additionally, the use of such a stream allows for the spent regenerant in some instances to be separated along with the reactor effluent.
[00024] With these general principles in mind, one or more embodiments of the present invention will be described with the understanding that the following description is not intended to be limiting.
[00025] As shown in the Figure, a feed stream 10 for a reaction zone, for example, an oligomerization zone 12 is first passed to a pretreatment zone 14 that includes various units 16a, 16b, 16c for removing contaminants. Other reaction zones may also be used. Although not required to be, the feed stream 10 is preferably a portion of a cracked effluent, for example, a portion of an effluent from a fluid catalytic cracking (FCC) process. The FCC process typically produces a significant quantity of light olefins, for example, the total yield of C4 and C5 olefins from an FCC unit can be 20 wt% or more of the fresh feed. The C4 and C5 olefins are typically low value products. Accordingly, there is often a desire to convert these olefins into more desired product like diesel via oligomerization. For a detailed explanation of an exemplary FCC unit, reference is made to U.S. Pat. Pub. No. 2014/01435552, the entirety of which is incorporated herein by reference. In this application, hydrocarbon molecules may be abbreviated CI, C2, C3 . . . Cn where "n" represents the number of carbon atoms in the one or more hydrocarbon molecules. Furthermore, a superscript "+" or "-" may be used with an abbreviated one or more hydrocarbons notation, e.g., C4+ or C4-, which is inclusive of the abbreviated one or more hydrocarbons. As an example, the abbreviation "C4+" means one or more hydrocarbon molecules of three carbon atoms and/or more.
[00026] In addition to C4/C5 olefins, the feed stream 10 may also include light hydrocarbons, for example C3 hydrocarbons, as well as heavier hydrocarbons, such as C6 to C7 hydrocarbons. The C4 hydrocarbons includes butenes, i.e., C4 olefins, and butanes. Butenes include normal butenes and isobutene. The C5 hydrocarbons includes pentenes, i.e., C5 olefins, and pentanes. Pentenes include normal pentenes and isopentenes. Typically, the feed stream 10 will comprise 20 to 80 wt% olefins and suitably 40 to 75 wt% olefins. In an aspect, 55 to 75 wt% of the olefins may be butenes and 25 to 45 wt% of the olefins may be
pentenes. Additionally, 10 wt%, suitably 20 wt%, typically 25 wt% and most typically 30 wt% of the feed may be C5 olefins. In addition to the hydrocarbons, the feed stream 10 includes sulfur compounds, di-olefins, oxygenates, nitriles, each of which is removed or converted in the units 16a, 16b, 16c in the pretreatment zone 14.
[00027] One of the units 16a, 16b 16c in the pretreatment zone 14 comprises a nitrile removal zone 18. Other units 16a, 16b in the pretreatment zone 14 may include a sulfur removal zone, a selective hydrogenation zone, a water wash, or a bisulfite wash.
[00028] The nitrile removal zone 18 is configured to selectively adsorb nitriles, and possibly some oxygenates, from the feed stream 10 (which may or may not have been subjected to pretreatment in other units 16a, 16b in the pretreatment zone 14) and provide a cleaned feed stream 20 that is relatively free of nitriles. The nitrile removal zone 18 can use any suitable adsorbent for removing nitriles from the feed stream 10, which can be, for example, a zeolitic molecular sieve. Generally, the molecular sieve can include a zeolite X, Y, L, or a combination thereof. In addition, the adsorption conditions can be 20 to 80 °C (68 to 176 °F) and a pressure of 100 to 3,500 kPa (14.5 to 508 psi). Exemplary adsorbent beds and conditions are disclosed in, e.g., U.S. Pat. No. 5,271 ,835.
[00029] The nitrile removal zone 18 may include one or more, preferably two or more, adsorbent beds. Preferably, the nitrile removal zone 18 includes two or three vessels arranged in a lead-lag configuration (not shown), allowing for the feed stream 10 to be processed in one vessel while adsorbent in a second vessel is being regenerated (discussed below).
[00030] The cleaned feed stream 20, directly or after one or more additional pretreatment processes to remove other contaminants, is passed to the oligomerization zone 12 which includes at least one oligomerization reactor 22 containing a catalyst and being configured to provide an oligomerized effluent 24. Although not depicted as such the cleaned feed stream 20 may be preheated before entering the oligomerization reactor 22.
[00031] The oligomerization reactor 22 may be an upflow reactor to provide a uniform feed front through the catalyst bed, but other flow arrangements are contemplated. In an aspect, the oligomerization reactor 22 may contain an additional bed or beds of oligomerization catalyst. In the oligomerization zone 12, C4 olefins in the cleaned feed stream 20 oligomerize over the oligomerization catalyst to provide an oligomerate comprising C4 olefin dimers and
trimers. Additionally, C5 olefins in the cleaned feed stream 20 oligomerize over the oligomerization catalyst to provide an oligomerate comprising C5 olefin dimers and trimers and co-oligomerize with C4 olefins to make C9 olefins. The oligomerization produces other oligomers with additional carbon numbers.
[00032] The operating conditions of the oligomerization zone 12 include exemplary operating pressures between 2.1 MPa (300 psia) and 10.5 MPa (1,520 psia), or between 2.1 MPa (300 psia) and 6.9 MPa (1,000 psia), or between 2.8 MPa (400 psia) and 4.1 MPa (600 psia). Lower pressures may be suitable if the reaction is kept in the liquid phase. The temperature of the oligomerization conditions in the oligomerization zone 12 expressed in terms of a maximum bed temperature is in a range between 150 and 300 °C (302 to 572 °F), or between 200 and 250 °C (392 to 482 °F), or between 225 and 245 °C (437 to 473 °F). The space velocity may be between 0.5 and 5.0 hr1. Across a single bed of oligomerization catalyst, the exothermic reaction will cause the temperature to rise. Consequently, the oligomerization reactor 22should be operated to allow the temperature at the outlet to be over 25 °C (45 °F) greater than the temperature at the inlet.
[00033] The oligomerized effluent 24 from the oligomerization zone 12 may be passed to a separation zone 26 having one or more separation vessels to provide various product streams. For example, the separation zone 26 may comprise two separation columns 28, 30, each of which is a fractionation column. As used herein, the term "column" means a distillation column or columns for separating one or more components of different volatilities. Unless otherwise indicated, each column includes a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottom stream back to the bottom of the column. Feeds to the columns may be preheated. The top pressure is the pressure of the overhead vapor at the outlet of the column. The bottom temperature is the liquid bottom outlet temperature. Overhead lines and bottom lines refer to the net lines from the column downstream of the reflux or reboil to the column.
[00034] A first separation column 28 may separate the oligomerized effluent 24 into an overhead stream 32 comprising C4 olefins and hydrocarbons and a liquid bottoms stream 34 comprising C5+ olefins and hydrocarbons. The liquid bottoms stream 34 may be passed to the
second fractionation column 30 to be separated into different streams, for example a gasoline stream 36, typically comprising C5 to C9 hydrocarbons, and a diesel range stream 38, typically comprising CI O to C16 hydrocarbons. The gasoline stream 36 and the diesel range stream 38 may be processed further, for example, the diesel range stream 38 being passed to a hydrotreating zone 39 to remove heteroatoms to provide a diesel fuel stream. As used herein, the term "diesel" can include hydrocarbons having a boiling point temperature in the range of 150 to 400 °C (302 to 752 °F) and preferably 200 to 400 °C (392 to 752 °F). As used herein, the term "gasoline" can include hydrocarbons having a boiling point temperature in the range of 25 to 200 °C (77 to 392 °F) and at atmospheric pressure.
[00035] The hydrotreating zone 39 includes a hydrotreating reactor 41. The hydrotreating zone 39 shown in the Figure has one hydrotreating reactor 41 ; however, more than one hydrotreating reactor 41 may be utilized. Each hydrotreating reactor 41 may have one or more beds 43a, 43b of a suitable hydroprocessing catalyst. A hydroprocessed diesel stream 45 exits the hydrotreating zone 39.
[00036] The hydrotreating reactor 41 in the hydrotreating zone 39 may be operated in a continuous liquid phase, in a continuous gas phase, or with a mixture of gas and liquid.
[00037] During the hydrotreating reactions occurring in the hydrotreating reactor 41 , hydrogen is necessarily consumed. Accordingly, the diesel range stream 38 may be mixed with a hydrogen stream 47 prior to entering the hydrotreating reactor 41. Additionally, hydrogen may be provided to the hydrotreating reactor 41 at one or more hydrogen inlet points (not shown) located downstream of the feed inlet for the diesel range stream 38. The flow rate of hydrogen added at these downstream locations is controlled to ensure that the reactor operates in a continuous liquid phase.
[00038] In some aspects, the diesel range stream 38 does not contain recycled product comprising a portion of the hydroprocessed diesel stream 45 or other hydrocarbon diluent. In other aspects, a recycle stream or diluent (both not shown) may be incorporated into the fresh diesel range stream 38 prior to hydrotreating to feed additional volume to the hydrotreating reactor 41 to provide added hydrogen-carrying capacity to the diesel range stream 38 or to provide additional mass to reduce the temperature rise in catalyst beds 43a, 43b. In such aspects, any recycled product or diluent typically is introduced into the diesel range stream 38
before the hydrogen in line 47 is mixed with the diesel range stream 38. Typically, such recycled product may be previously stripped of a vaporous hydrogen sulfide, nitrogen or nitrogen containing compositions, and any other vapor phase materials.
[00039] In the hydrotreating zone 39, hydrogen gas is contacted with the hydrocarbons in the diesel range stream 38 in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur and nitrogen from the hydrocarbon feedstock. Additionally, unsaturated hydrocarbons are saturated.
[00040] Suitable hydrotreating catalysts for use in the present invention are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and/or nickel and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina. Other suitable hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. It is within the scope of the present invention that more than one type of hydrotreating catalyst be used. The Group VIII metal is typically present in an amount ranging from 2 to 20 wt%, preferably from 4 to 12 wt%. The Group VI metal will typically be present in an amount ranging from 1 to 25 wt%, preferably from 2 to 25 wt%.
[00041] Suitable hydrotreating reaction conditions include a temperature from 204 to 482 °C (400 to 900 °F), preferably no more than 388 °C (730 °F), a pressure from 3.5 to 17.3 MPa (500 to 2500 psig), preferably no more than 10,342 kPa (1500 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous feedstock (i.e., the diesel range stream 38) from 0.1 hr"1 to 10 hr"1 with a hydrotreating catalyst or a combination of hydrotreating catalysts. In an aspect, the hydrotreated diesel stream 45 (i.e., the hydrotreated effluent) has a lower sulfur concentration and an improved cetane number than that of the diesel range stream 38. The further processing of the hydrotreated diesel stream 45 is not important to the practicing of the present invention.
[00042] Returning to the nitrile removal zone 18, eventually the adsorbent will be become spent, requiring regeneration to desorb the nitriles and regenerate the adsorbent. Accordingly, a regenerant stream 40 comprising a hot liquid is utilized to desorb the nitriles. By "hot" it is meant that the regenerant stream 40 has a temperature between 175 to 275 °C
(347 to 527 °F), or between 200 to 250 °C (392 to 482 °F), or 230 °C (446 °F). In the prior art designs, a regenerant stream comprised vapor, typically with C4/C5 hydrocarbons. Again, such a vapor stream may not be readily available; however, various hot liquid streams having low levels of nitriles are typically readily available in most refineries.
[00043] Accordingly, in one embodiment, the regenerant stream 40 may comprise a portion of the oligomerized effluent 24 without further conversion or treating. For example, the regenerant stream 40 may comprise a stream from the separation zone 26. In at least one embodiment, the regenerant stream 40 comprises a sidecut stream 42 from the second fractionation column 30 in the separation zone 26. Preferably, the sidecut stream 42 comprises a range of C8 to C12 hydrocarbons. However, in some instances, the use of the oligomerized effluent 24, or a portion thereof, may not be desirable, for example depending on the amount of dienes in the sidecut stream 42.
[00044] Accordingly, it is also contemplated that in one or more embodiments, at least a portion of a hydrotreated effluent is used as the regenerant stream 40. For example, a diesel fuel stream 44 from a hydrotreating unit (not shown) be used as the regenerant stream 40. It is contemplated that the diesel fuel stream 44 comprises at least a portion of the diesel range stream 38 that has been hydrotreated, such as the hydrotreated diesel stream 45 from the hydrotreating zone 39. Other readily available hot liquid streams may be used in accordance with the present invention as the regenerant stream 40.
[00045] A spent regenerant stream 46, including the desorbed nitriles, may be removed from the nitrile removal zone 18. In at least one embodiment, the spent regenerant 46 is combined and passed to the separation zone 26 along with the oligomerized effluent 24. Although it is depicted that the spent regenerant 46 and the oligomerized effluent 24 are combined, it is also contemplated that each is passed into the separation zone 26 independently.
[00046] In the depicted exemplary embodiment, the nitriles will separate out with the overhead stream 32 of the first fractionation column 28. The hydrocarbons in the regenerant, will mostly comprise components in the liquid bottoms stream 34 that can be processed and separated as described above.
[00047] Alternatively, in some embodiments, the nitriles in the spent regenerant stream 46 may be less than 100 ppm. In at least one embodiment, it is contemplated that the spent
regenerant 46 may be passed to a fuel blending pool (not shown). Furthermore, it is also contemplated that the spent regenerant 46 is passed to the hydrotreating zone 39.
[00048] In the present invention, various processes for regeneration for a nitrile removal zone are provided which utilize a readily available hot liquid regenerant. In addition to being more readily available that prior art streams, the use of the hot liquid may lower operating utilities since it will not need to be vaporized. In embodiments in which a portion of oligomerized effluent is used, the process will provide a readily available stream of hot liquid that is relatively free of contaminants. Additionally, in various embodiments, the use of the hot liquid allows for the use of existing equipment to separate nitriles from the liquid hydrocarbons of the regenerant.
SPECIFIC EMBODIMENTS
[00049] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
[00050] A first embodiment of the invention is a process for removing nitriles from a feed stream for a reaction zone, the process comprising adsorbing nitriles from a feed stream in a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; oligomerizing the cleaned feed stream in an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; and, desorbing the nitriles from the nitrile removal zone with a regenerant stream comprising a hot liquid to provide a spent regenerant stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a portion of the oligomerized effluent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a portion of a hydrotreated effluent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the feed stream comprises C3 to C7 hydrocarbons. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up
through the first embodiment in this paragraph further comprising separating the oligomerized effluent in a separation zone into a C4- stream, a diesel stream, and a gasoline stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the separation zone includes at least two columns and wherein a first column of the at least two columns provides the C4- stream and wherein a second column of the at least two columns provides the diesel stream and the gasoline stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the second column further provides the regenerant stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the regenerant stream comprises a sidecut stream from the second column, wherein the sidecut stream comprises C8 to C12 hydrocarbons. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising separating the spent regenerant stream into at least one stream with nitriles. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the spent regenerant stream is separated in a separation column with the oligomerized effluent.
[00051] A second embodiment of the invention is a process for removing nitriles from a feed stream for a reaction zone, the process comprising passing a feed stream comprising hydrocarbons and nitriles to a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles; passing the cleaned feed stream to an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; passing the oligomerized effluent to a separation zone being configured to provide at least one C4- stream and at least one product stream; and, passing a regenerant stream comprising a hot liquid to the nitrile removal zone to desorb the nitriles and provide a spent regenerant stream, the spent regenerant stream including nitriles. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the regenerant stream comprises a portion of a hydrotreated effluent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second
embodiment in this paragraph wherein the regenerant stream comprises a portion of the oligomerized effluent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the feed stream comprises a C3 to C7 hydrocarbon feed stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the separation zone comprises at least two columns, wherein a first column provides the C4- stream, and wherein a second column provides the at least one product stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the second column provides the regenerant stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising passing the spent regenerant stream to the first column of the separation zone. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the spent regenerant stream and the oligomerized effluent are combined before being passed into the first separation column. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the regenerant stream comprises a C8 to C12 hydrocarbon stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the feed stream comprises a portion of an effluent from a catalytic cracking zone.
[00052] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
[00053] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
[00054] It should be appreciated and understood by those of ordinary skill in the art that various other components such as valves, pumps, filters, coolers, etc. were not shown in the drawings as it is believed that the specifics of same are well within the knowledge of those of ordinary skill in the art and a description of same is not necessary for practicing or understanding the embodiments of the present invention.
[00055] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents.
Claims
1. A process for removing nitriles from a feed stream for a reaction zone, the process comprising:
adsorbing nitriles from a feed stream in a nitrile removal zone having an adsorbent configured to selectively adsorb nitriles from the feed stream and provide a cleaned feed stream relatively free of nitriles;
oligomerizing the cleaned feed stream in an oligomerization zone having a reactor containing a catalyst and configured to provide an oligomerized effluent; and,
desorbing the nitriles from the nitrile removal zone with a regenerant stream comprising a hot liquid to provide a spent regenerant stream.
2. The process of claim 1 wherein the regenerant stream comprises a portion of the oligomerized effluent.
3. The process of claim 1 wherein the regenerant stream comprises a portion of a hydrotreated effluent.
4. The process of any one of claims 1 to 3 wherein the feed stream comprises C3 to C7 hydrocarbons.
5. The process of claim 1 or 2 further comprising:
separating the oligomerized effluent in a separation zone into a C4- stream, a diesel stream, and a gasoline stream.
6. The process of claim 5 wherein the separation zone includes at least two columns and wherein a first column from the at least two columns provides the C4- stream and wherein a second column from the at least two columns provides the diesel stream and the gasoline stream.
7. The process of claim 6 wherein the second column further provides the regenerant stream.
8. The process of claim 7 wherein the regenerant stream comprises a sidecut stream from the second column, wherein the sidecut stream comprises C8 to C12 hydrocarbons.
9. The process of any one of claims 1 to 3 further comprising:
separating the spent regenerant stream into at least one stream with nitriles.
10. The process of claim 9 wherein the spent regenerant stream is separated in a separation column with the oligomerized effluent.
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Publication number | Priority date | Publication date | Assignee | Title |
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US6019887A (en) * | 1995-09-18 | 2000-02-01 | Intevep, S.A. | Nitrile selective removal process |
WO2013013885A2 (en) * | 2011-07-25 | 2013-01-31 | Exxonmobil Chemical Patents Inc. | Integrated nitrile poison adsorption and desorption system |
US20150159099A1 (en) * | 2013-12-05 | 2015-06-11 | Uop Llc | Light olefin oligomerization process for the production of liquid fuels from paraffins |
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WO2006084285A2 (en) * | 2005-01-31 | 2006-08-10 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization and biodegradable compositions therefrom |
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Publication number | Priority date | Publication date | Assignee | Title |
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US6019887A (en) * | 1995-09-18 | 2000-02-01 | Intevep, S.A. | Nitrile selective removal process |
WO2013013885A2 (en) * | 2011-07-25 | 2013-01-31 | Exxonmobil Chemical Patents Inc. | Integrated nitrile poison adsorption and desorption system |
US20150159099A1 (en) * | 2013-12-05 | 2015-06-11 | Uop Llc | Light olefin oligomerization process for the production of liquid fuels from paraffins |
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